Oil soluble acylated dye



\ 35 above.

. 45 method by which they can be 50 brace solubility in fats and fatty oils,

Patented July so, mo

; PATENT" OFFICE on. SOLUBLE ACYLATED DYE Anderson'W. Ralston and Robert J. Vander Wal,

Chicago,'lll., assignors to Armour and Company,

Chicago, 111., a corporation of Illinois No Drawing.

12 Claims.

This invention relates to oil-solubilized dyes and it comprises, as new materials organic dyes which have been rendered soluble in organic solvents, or whose solubility in organic solvents has been increased, by incorporating in the dye molecule one ormore acyl groups having the formula RCO- wherein R is a straight-chain alkyl radical containing at least eleven carbon atoms; and

it further comprises processes wherein organic dyes are reacted with higher fatty acid chlorides in the presence of aluminum. chloride by a Friedel-Crafts reaction and the intermediate aluminum chloride reaction product thus formed is hydrolyzed. 1

Organic dyes or coloring compounds used in the dyeing of fabrics, in textile printing pastes, and the like, are generally-soluble in water or in acid or alkali solutions used in the dye baths. These organic dyes are either insoluble, or are but sparingly soluble in most organic liquids such, for example, as beuzol, alcohol, chlorinated.

hydrocarbons, petroleum hydrocarbons, such as gasolene, kerosene and lubricating oils, solid or liquidfwaxes or wax compositions, soaps, plastics and the like. There are, of course, a few dyes available which can be added to 'gasolene for the purpose of imparting color thereto: or can be added to cosmetics, leather-coloring compounds, plastics and similar organic materials, but it is anobserved'fact that so-called oil-soluble" dyes is quite limited.

There is a large potential demand fororg'anic coloring materials which can be used to color organic products of the general kinds referred to The azo and triphenylmethane classes of dyes contain hundreds of colors which would find immediateapplication in the coloring of organic products, other than those of vegetable or animal fibre origin, if they were soluble 40 therein.

What is neededis some general method by which these generally oil-insoluble dyes can be rendered soluble, or, in the case of those which have some small degree of oil solubility, some rendered more soluble. By oil solubility we mean that the dye will dissolve in petroleum hydrocarbons, such as gasolene, kerosene. lubricating oils and even parafiin waxes. We also mean this term to emsuch as linedible oils, such in soaps of the vegew seed oil, and other vegetable oils, as cottonseed oil, and also table or animal fatty term "oil soluble is used by us in a generic sense to distinguish from those dyes which are gener- .the number of acids. Consequently, the

Application February 17, 1938, Serial No. 191,112

ally only soluble in The prior art also designates dyes as oil soluble as. distinguished from those dyes which are not soluble in "oily liquids and "waxy or grease-like solid materials.

Our invention is based upon the discovery that organic dyes whose structural configuration contains one or more closed ring radicals havingone or more replaceable hydrogen atoms thereon can be made to react with higher fatty acid chlorides by a typical Friedel-Crafts reaction to give derivatives wherein one or more ,of such hydrogens have been replaced by an acyl radical. Such derivatives can, in a sense, be defined broadly as ketonic since their structural configuration will contain a COR group derived from the fatty acid chloride. By introducing acyl groups having at least eleven carbon atoms in the alkyl radical we render the dye oil soluble.

Thus, for example, if we start with a very simple dye, such as Chrysoidine, first precipitating the dye base from the hydrochlorideby the addition of alkali and then reacting the dye base with stearyl chloride (stearic acid chloride) under Friedel-Crafts conditions we substitute stearyl groups for one or more of the hydrogen in the benzene rings' of this dye base. The stearyl groups cause the dye to become soluble in solvents, such as benzene, alcohol, petroleum ether, gasolene and the like. To put-it another way, our invention comprises incorporating acyl groups from higher fatty acids having at least twelve carbon atoms in normally oil insoluble dyes, or in'those which are but sparingly oil= soluble.

Our invention is broadly applicable to the preparation of acyl derivatives of any organic dye having hydrogens in a cyclic ring reactive with higher fatty acid chlorides. ,Thus, for example, we can form such acyl derivatives from the azo, triphenylmethane, and vat dyes. The only requirements are that there must be one or more reactive ring hydrogens capable of replacement by our particular acyl groups.

As acylating reagents we use any higher fatty 5 acid chloride' having at least twelve carbonatoms, or at least eleven carbon atoms in the alkyl group thereof. Generally, we find itadvantageous touse stearyl chloride but our invention is not limited thereto because we can use as the acylating reagent lauryl chloride, myristyl chloride, palmityl chloride, arachidyl "chloride behenyl chloride. oleyl chloride and linolenyl chloride.

2 chloride as a condensing agent in conformity with the usual Friedel-Crafts procedure. and the together under the usual chloride and 100 parts by petroleum ether and insoluble in water.

reaction mixture is conventional way.

The oil solubility imparted tothe dye or dye base will depend upon the proportion of the dye or dye base to the fatty acid other words, solubility increases as the number of acyl groups introduced increases. For this reason we find it advantageous to use a rather large, molecular excess of the fatty acid chloride in each instance. Thus in some cases the amount of fatty acid chloride is five or ten times the molecular proportion of the dye so that a number of the acyl groups are substituted in the molecule. The ultimate products are, as stated, ketones or polyketones'.

We shall now invention:

subjected to hydrolysis in the give examples of practising our Example 1 An orange monoazo dye, known commercially as Chrysoidine, is used. The formula for this dye is:

E The dye base is obtained by precipitation with alkali from a water solution. 4.2 parts by weight of this base, 45 parts of stearyl chloride and 2'7 parts of aluminum chloride, together with 100 parts, of dry carbon tetrachloride, are reacted Friedel-Crafts conditions. The temperature is kept at about 40 C. for one hour, during which time the addition of the aluminum chloride is completed. The reaction mixture is then hydrolyzed with ice and the product steam distilled to remove the solvent and complete the hydrolysis. The product is then extracted with sodium hydroxide solution to remove any stearic acid formed during the reaction. The product is ilnally crystallized from alcohol containing hydrochloric acid which purifies the dye it to its hydrochloride. The probable formula for the product is as follows, It being CnHss.

COR ROC COR NHl-HCI This product is soluble in benzene, alcohol and The product has a, waxy texture and solutions of it are strongly orange in color.

Example 2 A brown 'bisazo dye, Bismarck brown, is used. The formula for this dye is:

mnncl rhino-NH,

The free base is obtained by adding alkali to a water solution of the hydrochloride. 7 parts by weight of the dye base, 30 parts by weight of stearyl chloride, 14 parts by weight of aluminum weight of tetrachlorethane are reacted according to the conditions described under Example 1. The hydrolyzed product is a hard waxy solid soluble in benzene, carbon tetrachloride and alcohol. .It is miscible chloride used. In

base and at the same time converts with paraflin. Solutions of it probable formula is as follows,

ROC

6 parts by weight of the p stearyl chloride, 14 parts 100. parts tetrachlorethan HCLHsN C O R EGLHiN COR Example 3 A red triphenylmethane dye, p-fuchsine, is

this dye is:

are brown. The B being CrrHas.

' n nqnmnci on -fuchsine base, 12 parts aluminum chloride and e are reacted according to the conditions described under Example 1. After hydrolysis the product is crystallized from alcohol and treated wi hydrochloric acid to chloride. The

alcohol and petroleum ether and insoluble in water. The color in solu- It is soluble in tion is red.

W. B., is used. .EQIIOWS:

th an alcoholic solution of form the monohydroprobable formula of" this compound is as follows, R being CnHzm COR.

benzene,

Example 4 A- green triphenylmethane dry, Victoria Green The formula for-this dye is as CHI CHI

5 parts by weight of the dye base, 45 parts of stearyl chloride. and 50 parts of tetrachloreth a temperature of 35-40 cedure as described product after conver a gray-green powder acid and acetone to g It is colorless in melted upon cooling. The probable R being CrrHas.

under The dye is C. according Example 1. sion to thehy'clrochloride is soluble in alcohol, stearic ive a blue-green solution. paraffin but turns green 20 parts of aluminum chloride ane are reacted at to the pro- The final insoluble in water.

COB

formula of this dye is as follows,

Example 5 A violet triphenylmethane dye, 2B, is used. The formula for this 5 lows:

Methyl Violet dye is as fol- CHI H I Y\CH:

parts by weight of the dye base,'9 parts by weight of lauryl chloride, 6.5 parts of aluminum chloride and 100 parts of tetrachlorethane are 'reacted according to the conditions described under Example 1. The final product after conversion to the hydrochloride salt is a green waxy gasolene to all of which. it imparts an emerald green color. The product is insoluble in water. The color of the dye has apparently been changed during the reaction. The probable formula for this product is as follows, B being CnHn.

trample 6 A black nigrosine dye is used. this dye is as follows:

4 The formula for 5 parts by weight of this dye, 15 parts of stearyl chloride, 10 parts of aluminum chloride and 100 parts of-tetrachlorethane are reacted according to the conditions .described under Example. 1. After hydrolysis the product is dissolved in petroleum ether, 7 vent evaporated. The product is a black waxy solid soluble in benzene, petroleum ether and kerosene. It is slightly soluble in alcohol and completely insoluble in water. Its probable'formula is asfollows, It being cums.

I COR I 7 N I) Q1: Cl OR COR solid, soluble in benzene. alcohol, mineral oil and .formula for this dye is drochloride is soluble the solution filtered and the sol- I rivative of an aromatic gen atom replaceable of said replaceable Example 7 I -A red azine dye, phenosafranine, is used. The formula for-this dye is as follows:

I a NH:

6.4 parts of the dye base, 15 chloride, 15 parts of aluminum chloride and 100 parts of tetrachlorethane are reacted as above described. The product is a red solid soluble in alcohol, benzene and petroleum ether to which it imparts a red color. The probable formula is as follows, R'being CnHas. j

R o c 7 e Example 8 I A yellow acridine dye, proflavine, is used. The

as follows:

i 1 159mm The free base is obtained as previously described. 4 parts of the dye base, parts of stea -y] chlo-' ride, 21 parts of aluminum chloride and 100 parts of tetrachlorethane are reacted as previously de-' scribed." The product after conversion to the hyin alcohol, petroleum ether and benzene. Its probable formula is as follows, R being CuHas.

con con HGLNH N n-H01 on on increased byacylating the parts of stearyl phoric groups and having at least one nuclear aromatic nucleus containing at least one hydroby an acyl group which comprises reacting such chloridehaving at least twelve carbon atoms in i the presence of a Friedel-Crafts catalyst, hy-

drolyzing the intermediate Friedel-Crafts reaca dyewith a fatty acid tion product'thus formed, and recovering a dye I taining at least one acyl group having at least twelve carbon atoms substitutedfor at least one hydrogen atoms.

soluble in aliphatic hydrocarbon oils and con- 2. The process as in claim 1 wherein the fatty acid chloride is stear'yl chloride.

3. The process as in claim 1 wherein Friedel-Crafts catalyst is aluminum chloride.

4. The process as in claim 1 wherein the fatty acid chloride is stearyl chloride and the Friedel- Crafts catalyst is aluminum chloride.

5. The process of preparing an oil soluble azo dye which comprises reacting the-dye with a the 'fatty acid chloride containing at least twelve carbon atoms in the presence of a Friedel-Craf-ts catalyst," hydrolyzing the intermediate Friedel- Crafts reaction product, and recovering an azo dye soluble in'aliphatic hydrocarbon oils and containing at least one acyl group having at least twelve carbon atoms substituted for one of the cyclic hydrogens of said azo dye.

6. The process asin claim 5 wherein the fatty acid chloride is stearyl chloride.

7. The process as in claim 5 wherein the Friedel-Crafts catalyst is aluminum chloride.

8. Theprocess as in claim 5 wherein the fatty acid chloride is stearyl chloride and the Friedel- Crafts catalyst is aluminum chloride.

9. The process of preparing an oil soluble triphenylmethane dye which comprises reacting the dye with a fatty acid chloride containing at least twelve carbon atoms in the presence of a Friedel- Crafts catalyst, hydrolyzing the intermediate Friedel-Crafts reaction product, and recoveringpa triphenylmethane dye soluble in aliphatic hydrocarbon oils and containing at least one acyl group having at least twelve carbon atoms substituted 

